Results: T0 median urinary TBA and DET was <0.25 ug/L in all subjects; in farmers urinary DET significantly increased to 1.81 and 2.95 ug/L at T1 and T2, respectively (p<0.001), urinary TBA was always <0.25 ug/L. Hair DET was always <0.010 ng/mg. T0 median TBA in urban residents was <0.010 ng/mg hair, such level was lower than 0.010 ng/mg measured in both farmers and in rural residents (p=0.004). ES median TBA was 0.073>0.011>0.010 ng/mg hair in farmers, rural residents and urban residents, respectively (p<0.001). No correlation was observed between urinary DET and hair TBA, while significant or borderline significant correlations were found between hair TBA and age or application time (p = 0.021 and p 0.081). Conclusions: Urinary DET and hair TBA seem to be promising candidates for biomonitoring short- and long-term exposure to TBA. The use of this herbicide in agriculture impacts the exposure of rural residents.